US1309623A

US1309623A - Catalyzes

Info

Publication number: US1309623A
Authority: US
Publication date: 1919-07-15
Anticipated expiration: 1936-07-15

Description

A. HENWOOD.

CATALYZER.

APPLICATION FILED JUNE 25.1918.

1 309,623. Patented July 15, 1919.

F/GJ.

JTTORA EY.

,di erent nmmnnm HENWOOD, or CYNWYD, PENNSYLVANIA.

' carnmrznn.

Specification of Letters Patent.

Patented July 15, 1919.

Application filed June 25. 1918. Serial No. 241,724.

To all who/11,176 may concern:

Be it known that I, ABRAHAM HENWOOD, a citizen of the United States, residin at Cynwyd, county of Montgomery, and tate of.Pennsylvania, have invented a new and useful Improvement in Catalyzers, of which the followin is a full, clear, and exact description, re erence being had to the accompanying drawings, which form a part of this specification.

In any process for effecting a chemical combination of gases by catalysis, as, for example, the formation of nitric acid from ammonia and oxygen, or of sulfuric anhydrid from sulfurous anhydrid and oxygen, it is recognized that the chemical action takes place at the surface of the catalytic material. When, therefore, the catalytic material is expensive or difficult to obtain, it is obviously desirable that it should present to the gases to be combined the greatest possible area proportionate to its bulk.

There are other reasons which imperatively require the avoidance of a superfluous bulk of the catalytic material. Thus, the tendency is for the catalyzer to become very highly heated during the reaction, and even at a moderately high temperature the prodnot of the reaction decomposes as lllustrated, in the case of nitric acid, by the following equation:

Assuming a catalyzer of requisite activity, such as platinum, the greater its bulk or mass, the greater its capacity for holding heat; and hence the higher the temperature the greater the decomposition.

The art has recognized the advisability of presenting a relatively large surface of catal ic material to the gases to be combine but has efleeted no more than an approach toward the ideal condition, and in some instances the object sought has been partially attained only at the expense of creating other deleterious conditlons obstructive of successful operation. A few exam les will suffice.

latinum and other metals have been used as atalyze'rs in the shape of fine screens. Such catalyzers have the advantage of a uniform distribution of the orifices throu h which the gases pass, thereby largely avoidin the unequal elevation of temperature in arts of the catalyzer; but however fine t e mesh may practically be, it is clear that a large part of the catalytic material is not at the surface and therefore is practically inert. But such inactive part of the material acts to absorb and retain heat, and hence the temperature elevation exceeds the safe minimum. Moreover where latinum is employed, the cost of the material is excessive. These objections apply with still greater force where the gases are passed through a tube of platinum contained within a tube of alundum.

One of the most efficient catalyzers known in the sulfuric acid contact recess is that formed by the deposition 0 platinum on granular magnesium sulfate or other salt or mixture of salts. In the preparation of this catalyzer, however, it is found impossible to even approximatel completely coat the granular base, the p atinum being deposited discontinuously so as to cover actually a relatively small part of the surface of the grains, thus not only necessitating the use of a considerable bulk of the material, but reducing the efficiency of the catalyzer, in that the reacting gases cannot pass through the salts without contacting with a relatively large surface of inert or noncatalytic material. The same objections apply to a catalyzer formed by the deposition of nickel on finely divided charcoal.

Platinum sponge in such bulk as to be selfsustaining has also been proposed, and is an efficient catalyzer, but it is open, in less degree, to the objections applicable to platinum screens, in that a large proportion of the mass is below the surface and inactive. Substantially the same objections apply to a mixture of thorium oxid and radio active pranium oxid applied to fire clay or porce Platinized asbestos has also been successfully employed, but the asbestos, like the magnesium salts, has been coated in a pronouncedly discontinuous manner. Platinized porous clay has also been proposed, but is open to the same objection. Another objectlo'n common to platinized asbestos and platinum sponge (as ordinarily used) and other catalyzers is that the interstices are not regularly distributed and a larger volume of gases passes through the wider channels than through the more restricted ones, thereby causin an unequal heating of the mass, and ren ering it impossible to maintain the whole mass at any uniform temperature and therefore making it impossible to be applied in various ways,

hold the whole mass at the relatively low temperature required'to prevent partial decomposition.

The obj oct of my invention is to prepare a continuous porous or permeable contact or reaction surface, or diaphragm, of catalytic material, preferably -iplatinum, -.over .or through which all the gases must pass,

and which is distributed uniformly over the surface of a porous or permeable material which is. preferably non-metallic, non-catalytic, and a poorconductor of heat.

A base or support of suchmaterial of any suitable shape, so covered with a coating, film or'diaphragm of platinum, is placed in the channel provided for the reaction gases so that the latter must pass over or through the same and hence be brought into reactive contact with the continuous surface of platinum. Thus I attain maximum ec0n omy, even distribution, minimum mass and uniform temperature, and insure that practically every molecule of the reaction gases will be subjected, and in the same degree, to the influence ofthe catalyzer.

In preparing my improved catalyzer, I take a support, whichmay be in the shape of a disk,- hcmisphere, tube, orany other shape, made of porous or permeable material, such as alundum or silica. lyticmaterial, preferably platinum, is deposited, formed or placed, on either or both surfaces of'the su port, but preferably only on one surface. he catalytic material may as by impregnating with .suitable materials together with surface application of a supplemental mate rial, by spraying, or otherwise, followed, when necessary, by chemical reaction ofv the materials used by the application of heat or by the action of reducing agents, gaseous or in solution, so that there results a continuous ,coating or surface of the desired catalytic materialof regulated and desired thickness.

A preferred procedure isto soak an alum- ;dum support in ammonium chlorid, dry it, remove any excess from the surface, spray upon the surface a platmum chlorid so lution, thereby forming on the surface aprocipit-ate of ammonium chlorplatinare, and then dry and ignite, ,thus burning offor volatilizing ammonia, hydrogen chlorid, steam and chlorin, and leaving a superficial layer of platinum sponge.

The only serious. difficulty presented.

' the use of a oatalyzer of this character is the provision of means to prevent cracking. of the support due to expansion and contraction resulting from variation of temperature at the beginning and end of a run, .I have overcome this difiiculty by several expedi ents presentin decidedly pre and of a mass so small as not to be self-sustaining "The cata- .be of silica, is madein thes features in commonjthe one erred being the sealingof the catalytic support means-of a-plastic lute,

(pm-posed of a vitreous substance of the proper degree of viscosity at the worklng tempera- This, while providing an allows the support to expand ,The drawings show several embodiments of the invention, so far as it is capable of beingillustrated by drawings:

Figure 1 is a vertical section through a gas passage containing one form of catalyzer embodying my invention. Fig. 2 is a plan view of the bottom of the reaction chamber.

.Fig. 3 is a vertical sectional view showing another form of the invention. Fig. 4 is a similar view showing a third form.

Referring'first to Figs. 1 and 2; Through a base a provided with two concentric grooves b and 0 extends an nlet pipe (1,

through which are admittedthe gases of reaction. A catalyzer support e,} of inverted cup shape, coated, on its inside with catalytic material as above described, rests in the inner groove. .The support'rhay be composed of alundum. A cover 7, of pyrex lass, overliesand surrounds',., and is space from, ,the support e, and rests. in thegroove 0.

outlet pipe 9 for the product of the reaction extends through the base a and communicates with the space between, the cover f and support 6. ,.A hoo'd'or deflector h is placed over the. mouth ofthe inlet pipe d to;dis

tribute the enteringgases within the chamber inclosed by the-support e preparatory to their passage through the cu Neither thecup 6 nor the cover f is rigi ly attached to the base of its groove or of :the groove, but is embedded in a plastic to the side walls lute z'. of boric acid or other substance .x'vhich,

while providing an henneticalseal,-allows the, cup or cover to expand or contract. In other words, ithe supported edg eiof the cup or cover is not su portedor sealed rigidly, but is held'fiexiby. .1 prefer-.to'flow the boric acid over the surface of the base so that it will fillcand, overflow the grooves and provide a protective covering ,o'r enamel'for the bottom of the reaction chamber. "Boric acid is well adapted for. use either {in the formation of nitric acid or .sulfuric.acid. It is plastic, vitreous, has-a high degree of viscosity within the range of working temperatures, and is chemically'inert to ammonia and acids. The invention is not limited, however, to the use of boric; acid, as othersubstances are available.

In Fig. 3 the catalyzer su f ort, which may ar fa'flis i having a depending circumferential." resting in a groove it formed in-the wall of the reaction chamber or chari-nlel" L' ihe channel Z may be made of iron with'ji'tslinner wall enameled. The groove k contains a plastic lute m.

in ri 4, the catalyzer suppo t e i bf its inverted cup-shape, as in Fig. 1, its lower edge extending into a groove p formed by bending out the lower edge of an inwardl anddownwardly bent extension '1' of the wa l of the reaction chamber 8. The groove 1) contains a rigid cement t. In this modification. while the lute is rigid, the extension 1' is sufficiently thin to have enough inherent elasticity to allow the support 0 to expand and contract.

This invention contains subject-matter disclosed in my application Serial No. 179,.Q0i, filed July 11, 1017. Nothing therein claimed is claimed herein. Nor do I claim herein the herein described processes of catalytically combining gases and particularly oxidizing ammonia to nitric acid, as these form the subject-matter of applica tions Serial No. 243,758, filed July 8, 1918, and Serial No. 270,410, filed January 9, 1918.

Having now fully described my invention, what I claim and desire to protect by Letters Patent is 1. Means for catalytically combining gases comprising a gas passage and a catalytic structure consisting of a poroussupport presenting an extended surface and spanning the passage in such manner as to compel the gases to pass through it and a permeable catalyzer distributed over the surface of the support and through which also the gases are compelled to pass, the catalyzer presenting a substantially continuous surface and of negligible thickness, whereby practically its entire catalytic mass is rendered active.

2. Means for catalytically combining gases comprising a gas passage and a diahragm of catalytic material so positioned in the passage as to compel the gases to pass therethrough and of such negligible thickness that substantially the entire mass of the catalytic is active.

3. Means for catalytically combining gases comprising a gas passa e and a substantially continuous permeable diaphragm consisting wholly of platinum sponge so positioned in said passage as to compel the gases to pass therethrough.

4. Means for catalytically combining gases comprising a gas passage and a catalyzer therein consisting of a porous dlaphragm presenting an extended and substantially continuous surface of such negligible thickness that substantially the entire mass is active.

5. Means for eatalytically combining gases comprising a gas passage and a catalytic structure so positioned in the passage as to compel the gases to pass therethrough, said catalytic structure consisting of a porous catalyzer support presenting an extended surface and a permeable catalyzer distributed over the surface of the support of such negligible thickness that substantially the entire mass of the catalyzcr is active.

6. The combination with means forming a passage for reaction gases, of a rigid porous catalyzcr support closing said passage and therefore compelling the gases to pass through the support, and a permeable cata lyzer distributed substantially continuously over the surface of the support in the path of the gases and of such negligible thickness that substantially the entire mass of the catalyzer is active.

7. Means for catalytically combining gases comprising a gas passage, a porous non-catalytic support and a permeable layer consisting wholly of platinum sponge held superficially on the support, the latter being so positioned in said passage as to compel the gases to pass through both the support and the catalyzer.

8. The combination with a rigid eatalyzer support, of means to retain the support, adapted to yield or flex to allow f r the expansion and contraction of the support.

9. The combination with a rigid catalyzer support, of retaininn means for the support comprising a lute oi plastic material having Suflicient viscosity to allow for the expansion and contraction of the support.

10. The combination with a rigid catalyzer support, of means forming a groove to receive the edge ofthe support, and plastic viscous material within the groove and inclosing said edge.

11. The combination with a gas reaction passage, of a porous catalyzer support extending across said assage, and means retaining the edge of the support and adapted to yield or flex as the support expands or contracts. 0

12. The combination with a gas reaction pamage, of a porous catalyzer support extending across said passage, and means comprising plastic and viscous material closing the passage against the How of gases around the support and flexibly retaining the support to allow for its contraction and expansion.

In testimony of which invention I have hereunto set my hand, at Philadelphia, on this 22nd day of June, 1918.

ABRAHAM HENWOOD.